EP0290901B1 - Acides décane dicarboxyliques bicycliques, leur procédé de préparation et leur utilisation comme agents de flottation - Google Patents

Acides décane dicarboxyliques bicycliques, leur procédé de préparation et leur utilisation comme agents de flottation Download PDF

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Publication number
EP0290901B1
EP0290901B1 EP88107008A EP88107008A EP0290901B1 EP 0290901 B1 EP0290901 B1 EP 0290901B1 EP 88107008 A EP88107008 A EP 88107008A EP 88107008 A EP88107008 A EP 88107008A EP 0290901 B1 EP0290901 B1 EP 0290901B1
Authority
EP
European Patent Office
Prior art keywords
bicyclic
saturated
acids
branched
dicyclopentadiene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP88107008A
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German (de)
English (en)
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EP0290901A1 (fr
Inventor
Horst Dr. Eierdanz
Paul Dr. Schulz
Wolfgang Dr. Von Rybinski
Rita Köster
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0290901A1 publication Critical patent/EP0290901A1/fr
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Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C62/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C62/08—Saturated compounds containing ether groups, groups, groups, or groups
    • C07C62/12—Saturated compounds containing ether groups, groups, groups, or groups polycyclic
    • C07C62/14—Saturated compounds containing ether groups, groups, groups, or groups polycyclic having a carboxyl group on a condensed ring system
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/008—Organic compounds containing oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/02—Collectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; specified applications
    • B03D2203/02—Ores
    • B03D2203/04—Non-sulfide ores

Definitions

  • Dicarboxylic acids based on fatty substances for example the so-called dimer fatty acids, are important compounds with a large number of possible uses, cf. Polymers Paint Color Journal, Europ. Supplement, 1985 , 115. The favorable properties of this class of substances are based essentially on the presence of long alkyl chains. However, dicarboxylic acids with more than 12 carbon atoms can only be prepared by a few reactions.
  • the dimerization of unsaturated fatty acids leads to the above-mentioned dimer fatty acids with 36 carbon atoms.
  • the reaction of fatty acids with acrylic acid leads to a C21 dicarboxylic acid, see. IAOCS 57 , 219 (1975).
  • the hydrocarboxylation of unsaturated fatty acids gives C19 dicarboxylic acids, see. Fette, Seifen, Anstrichstoff 87 , 400 (1985).
  • Starting material for the preparation of the bicyclic decanedicarboxylic acids according to the invention are dicyclopentadiene and linear or branched, saturated alcohols having 1 to 22 carbon atoms, e.g. B. methanol, ethanol, n-propanol, i-propanol, n-butanol and its isomers, 2-ethylhexanol, branched octanols and fatty alcohols with 8th up to 18 carbon atoms, also in the form of their technical mixtures as they occur in the synthesis of fatty alcohols.
  • Bicyclic decanedicarboxylic acids which have an ether substituent are obtained.
  • linear or branched, saturated fatty acids can be reacted with dicyclopentadiene instead of the abovementioned alcohols, for.
  • Fatty acid mixtures can also be used, such as those obtained when animal or vegetable fats are split. In this way, bicyclic decanedicarboxylic acids which are substituted by an ester function can be prepared in this way.
  • bicyclic decanedicarboxylic acids can also be prepared starting from dicyclopentadiene and polyalkoxylated fatty alcohols; the fatty alcohols can have the meanings given above, but those with 8 to 18 carbon atoms are preferred, also in the form of their technical mixtures, as can be obtained from animal or vegetable fats.
  • These fatty alcohols are used in the form of their ethoxylated and / or propoxylated derivatives, where they are formally reacted with 1 to 25, preferably with 2 to 10, ethylene oxide and / or propylene oxide units. Ethylene oxide and propylene oxide units can have a random or block distribution.
  • the invention further relates to a process for the preparation of bicyclic decanedicarboxylic acids, which is characterized in that dicyclopentadiene with a compound of the general formula R-OH, in which R is defined as above is reacted and the bicyclic compound obtained is oxidatively cleaved at the double bond of the five-membered ring.
  • the oxidative cleavage of the double bond of the five-membered ring can be carried out by numerous methods known per se, e.g. B. by ozonolysis (K. Griesbaum, Fuel Chemistry 50 , 212 (1969)), by cleavage with permanganate or periodate (Can. J. Chem. 33 , 1714 (1955)), by reaction with peracids in the presence of ruthenium trichloride ( DE-A 21 06 307), by reaction with ruthenium oxide, acetaldehyde and oxygen (EP-A 0 021 118), by oxidation with oxygen in the presence of acetaldehyde and compounds of V, Mo, W or Os (US Pat. No.
  • the double bond can also be cleaved to form dicarboxylic acids by conventional methods (FD Gunstone, Hydroxylation Methods, Advances in Organic Chemistry, Volume I, Interscience Publishers, pp. 103 ff, 1960) produces the diol and cleaves it to the carboxylic acid, cf. also DE-OS 20 52 815, 21 06 913 (reaction with oxygen, peracetic acid in the presence of cobalt (II) acetate), and DE-OS 20 35 558 (reaction with peracetic acid in the presence of Ni, Fe, Pd, Mn or Co compounds).
  • the invention further relates to the use of the bicyclic decanedicarboxylic acids as flotation aids.
  • a stainless steel column (3 mx 40 mm) with Mellapack filling was fed continuously from top to bottom in direct current: 5000 g / h of a 20% solution of the bicyclic ether obtained according to the above working instructions a) in caprylic acid; 1000 g / h of water which was added to the olefin solution in a static mixer shortly before entering the column, 8 m3 / h ozonized air (approx. 160 g ozone / h, ie a 10% excess, based on the olefin).
  • the enthalpy of reaction was removed by evaporation of water in the carrier gas stream; the stationary ozonolysis temperature was approx. 36 ° C at the column inlet and approx. 20 ° C at the outlet.
  • the ozonide solution was separated from the residues of the aqueous phase (approx. 250 g / h) and worked up without intermediate storage.
  • the workup was carried out discontinuously.
  • the solution was autocatalytically oxidized in a glass or enameled reaction apparatus with intensive stirring at 80 ° C., with introduction of air saturated with water vapor at 60 ° C. (approx. 70 l / h / kg reaction mixture) for 1.5 hours.
  • the reactor contents were heated to 100 ° C. in 30 minutes and stirred for 1 hour with the addition of a further 28.5 g of H2O2 (70%) to 1 kg of organic phase.
  • the air supply was interrupted.
  • the temperature was raised from 100 to 130 ° C. in about 1 hour while discharging a distillate consisting mainly of water.
  • the final temperature was kept constant up to a peroxide number of the organic solution of approx. 10 units at 130 ° C. (0.5 to 1 h).
  • the fully reacted solution was storable.
  • the caprylic acid was removed at 2 mbar (heat transfer temperature 165 ° C.) on a thin-film evaporator, the residue was taken up in hot glacial acetic acid and crystallized with stirring and cooling.
  • the product was obtained in the form of small colorless crystals, mp 101-108 ° C., acid number 292. Further product could be obtained by concentrating the mother liquors. Overall yield 85%.
  • the compounds of the invention were tested for suitability as flotation aids.
  • the flotation experiments were carried out in a modified Hallimond tube (microflotation cell) according to B. Dobias, Colloid & Polymer Sci. 259 (1981), pages 775 to 776, at 23 ° C.
  • the individual tests were carried out with 2 g ore each. Distilled water was used to prepare the slurry. Sufficient collectors were added to the turbidity in each case so that a collector quantity of 500 g / t was available.
  • the conditioning time was 15 minutes each.
  • During the flotation a flow of air was passed through the slurry at a flow rate of 4 ml / min. The flotation time was 2 min in all experiments.
  • the results of the flotation tests are shown in Table II below.
  • the first column identifies the compounds of the invention used as collectors.
  • the total yield based on the total amount of ore
  • the metal yield based on the total amount of WO3 present in the ore.
  • the WO3, CaO and SiO2 contents of the respective concentrates are shown.
  • the flotation task had the following grain size distribution: 30% ⁇ 25 m 45% 25-100 m 24% 100-200 m
  • the compounds of the invention cause - as can be seen from the table - a satisfactory to excellent enrichment of WO3 in the concentrate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (5)

  1. Acides décanedicarboxyliques bicycliques pouvant être obtenus
    a) en faisant réagir en présence de catalyseurs acides du dicyclopentadiène avec un composé de formule (I),



            R-OH   (I)



    dans lequel R est choisi dans le groupe comportant
    i) des restes alkyle saturés, à chaîne linéaire ou ramifiée, avec 1 à 22 atomes de carbone,
    ii) des restes acyle saturés, à chaîne linéaire ou ramifiée, avec 2 à 34 atomes de carbone,
    iii) des restes d'alcools gras polyalcoxylés de formule (II)



            R¹O-(CH₂CHR²O)n-CH₂CHR²⁻   (II)



    dans laquelle R¹ signifie un reste d'alcool gras saturé avec 2 à 22 atomes de carbone, R² signifie l'hydrogène et/ou un reste méthyle et n signifie un nombre de 0 à 24,
    et
    b) scission par oxydation du composé bicyclique obtenu, à la double liaison du cycle à cinq chaînons.
  2. Procédé pour la fabrication d'acides décanedicarboxyliques bicycliques, caractérisé en ce que l'on fait réagir le dicyclopentadiène en présence d'acides avec un composé de formule (I)



            R-OH   (I)



    dans lequel R est choisi dans le groupe comportant
    i) des restes alkyle saturés, à chaîne linéaire ou ramifiée, avec 1 à 22 atomes de carbone,
    ii) des restes acyle saturés, à chaîne linéaire ou ramifiée, avec 2 à 34 atomes de carbone,
    iii) des restes d'alcools gras polyalcoxylés de formule (II)



            R¹O-(CH₂CHR²O)n-CH₂CHR²-   (II)



    dans laquelle R¹ signifie un reste d'alcool gras saturé avec 2 à 22 atomes de carbone, R² signifie l'hydrogène et/ou un reste méthyle et n signifie un nombre de 0 à 24,
    et qu'on scinde le composé bicyclique par oxydation, à l'endroit de la double liaison du cycle à cinq chaînons.
  3. Procédé selon l'une des revendications 2 à 3, caractérisé en ce que la scission par oxydation est effectuée de manière connue en soi avec de l'ozone.
  4. Procédé selon l'une des revendications 2 à 4, caractérisé en ce que la scission par oxydation est effectuée de manière connue en soi avec du permanganate de potassium.
  5. Utilisation des acides décanedicarboxyliques bicycliques selon la revendication 1 comme adjuvants de flottation.
EP88107008A 1987-05-11 1988-05-02 Acides décane dicarboxyliques bicycliques, leur procédé de préparation et leur utilisation comme agents de flottation Expired - Lifetime EP0290901B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873715613 DE3715613A1 (de) 1987-05-11 1987-05-11 Bicyclische decandicarbonsaeuren, verfahren zu ihrer herstellung und ihre verwendung als flotationshilfsmittel
DE3715613 1987-05-11

Publications (2)

Publication Number Publication Date
EP0290901A1 EP0290901A1 (fr) 1988-11-17
EP0290901B1 true EP0290901B1 (fr) 1993-03-24

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EP88107008A Expired - Lifetime EP0290901B1 (fr) 1987-05-11 1988-05-02 Acides décane dicarboxyliques bicycliques, leur procédé de préparation et leur utilisation comme agents de flottation

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US (1) US4956124A (fr)
EP (1) EP0290901B1 (fr)
JP (1) JPS63303946A (fr)
DE (2) DE3715613A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999023056A1 (fr) * 1997-11-05 1999-05-14 Susanna Askanazovna Saakian Nouveaux medicaments anti-convulsions
US9539587B1 (en) 2016-04-05 2017-01-10 Chevron Phillips Chemical Company Lp Mercaptanized dicyclopentadiene compositions and use thereof as a mining chemical collector

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2265601A (en) * 1940-12-30 1941-12-09 Permo Products Corp Recording stylus
US2323861A (en) * 1942-11-21 1943-07-06 Tide Water Associated Oil Comp Synthesis of organic acids
US2395452A (en) * 1943-02-20 1946-02-26 Resinous Prod & Chemical Co Esters of hydroxydihydronorpolycyclopentadienes
US2394582A (en) * 1943-02-20 1946-02-12 Resinous Prod & Chemical Co Ethers-of hydroxydihydronorpolycyclopentadienes
FR981609A (fr) * 1949-01-03 1951-05-29 Houilleres Bassin Du Nord Procédé de préparation de l'acide adipique
US3065192A (en) * 1959-02-18 1962-11-20 Exxon Research Engineering Co Light-stabilized polyvinylchloride formulation
GB1068905A (en) * 1963-04-22 1967-05-17 Ici Ltd Process for the manufacture of adipic acid
US3287395A (en) * 1963-05-02 1966-11-22 Pittsburgh Plate Glass Co Diels-alder reaction products
US3278580A (en) * 1963-08-15 1966-10-11 Hooker Chemical Corp Ether-alcohol containing esters of polyhalo-bicycloheptene dicarboxylic acids
US3646113A (en) * 1964-10-16 1972-02-29 Union Carbide Corp Bicyclo(2.2.1)hept-5(6)-yl compounds
US3364047A (en) * 1965-12-13 1968-01-16 Union Carbide Corp Esters of polyether-polyols and curable compositions thereof
DE2035558A1 (de) * 1970-07-17 1972-01-20 Deutsche Gold u Silber Scheide anstalt, vormals Roessler, 6000 Frank fürt Verfahren zur Oxydation vicinaler Diolgruppen
US3786068A (en) * 1970-08-24 1974-01-15 Upjohn Co Intermediate in the total synthesis of elenolic acid
DE2106307A1 (en) * 1971-02-10 1972-08-31 Percarboxylic acid oxidising agents - for unsatd org acid or vicinal dihydroxy cpd oxidn using ruthenium catalysts
US3701804A (en) * 1971-03-19 1972-10-31 Du Pont Process for adipic acid manufacture
US4166915A (en) * 1977-12-14 1979-09-04 The Dow Chemical Company Process for the preparation of endo-6-hydroxybicyclo[2.2.1]heptane-endo-2-methanol and derivatives thereof
US4144244A (en) * 1977-12-27 1979-03-13 Ciba-Geigy Corporation Perfluoroalkyl-iodo norbornane dicarboxylic acids and derivatives thereof
DE3065871D1 (en) * 1979-06-06 1984-01-19 Mitsui Petrochemical Ind Liquid phase catalytic co-oxidation of unsaturated compounds and aldehydes or ketones

Also Published As

Publication number Publication date
DE3879542D1 (de) 1993-04-29
EP0290901A1 (fr) 1988-11-17
JPS63303946A (ja) 1988-12-12
DE3715613A1 (de) 1988-11-24
US4956124A (en) 1990-09-11

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